High temperature bio-char carbonization and micron grinding and classification for inclusion into master batch polymerization

ABSTRACT

A thermal process for carbonizing hemp and reducing particle size, mechanically, by grinding or milling said carbonized hemp materials to generate a precise particle size hemp char and combining the hemp char particles with a polymer into a master batch.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of U.S. patent applicationSer. No. 16/811,719 filed on Mar. 6, 2020, which is a continuation ofU.S. patent application Ser. No. 16/395,515 filed on Apr. 26, 2019,which claims the benefit of U.S. Provisional Patent Application No.62/663,731 filed on Apr. 27, 2018, and U.S. Provisional PatentApplication No. 62/790,722 filed on Jan. 10, 2019, with the UnitedStates Patent and Trademark Office, the contents of which areincorporated herein by reference in their entirety.

FIELD OF THE INVENTION

The present application is generally related to processes and methodsfor forming charred or carbonized hemp-based materials capable of beingutilized in master batch processes with the charred materials havingenhanced physical properties and/or conductive properties for use infibers and other materials, through the formation of micron-sizedcarbonized particles.

BACKGROUND OF THE INVENTION

Char is made by heating a cellulosic material in a low oxygenenvironment at a temperature of between 600-700° C., with highertemperatures unnecessary for current processing needs. This processtypically takes between 12-72 hours, though longer periods are possible,and the process burns off volatile compounds such as water, methane,hydrogen, and tar. In commercial processing, the burning takes place inlarge concrete or steel silos with very little oxygen, and the burningstops before the material turns to ash. The process leaves black lumpsand powder, about 25% of the original weight.

Historically, char referred to charcoal, which was used for cooking andheating. The process of making charcoal is ancient, with archaeologicalevidence of charcoal production going back about 30,000 years. Makingcharcoal is modernly practiced throughout the world. Indeed, individualsutilize cellulosic matter, which is burned or charred at low oxygenconditions, to generate charcoal. When ignited, the carbon in charcoalcombines with oxygen and forms carbon dioxide, carbon monoxide, water,other gases, and significant quantities of energy. The quantity ofenergy is the salient feature as charcoal packs more potential energyper ounce than raw wood. Furthermore, charcoal burns steady, hot, andproduces less smoke and fewer dangerous vapors. Because charcoal burnshotter, cleaner, and more evenly than wood, it was used by smelters formelting iron ore in blast furnaces, and blacksmiths who formed andshaped steel, among other uses.

Many societies around the world use charcoal for cooking and heatingpurposes when no other heat sources are readily available. Even inmodern metropolises, hardwood lump charcoal is fashionable for the samereasons that “organic” food is fashionable, and it has obtained an auraof being more natural, has increased flavor, and is a better way tocook. There are more than 75 brands of charcoal and some are evenvarietal including: cherry, mesquite, coconut shell, tamarind, etc. Eachof these varietals are essentially identical, except for their plantorigins and traces of oils defining their unique scents and raw sourcematerial.

Hardwood lump charcoal is frequently made from hardwood scrap fromsawmills and from flooring, furniture, and building materialsmanufacturers. However, absent such scrap material, sources ofteninclude branches, twigs, blocks, trim, and other scraps for generatingthe material. The result of such variety of material is lumps that areirregular in size, often looking like limbs and lumber. Often, thismaterial is carbonized to different degrees because the different sizedlumps lead to slight differences in burn and temperature among thematerials. Lump is particularly valued for cooking as it leaves littleash since there are no binders as with manufactured charcoal, thusleaving a cleaner product than manufactured charcoal, and supposedlyprovides natural flavors for cooking. Certain charcoals containadditional fillers or accelerators, to aid in combustion, while others,e.g., binchotan, burn at much higher temperatures due to its particularprocessing.

Interestingly, as wood and other cellulosic materials are carbonized,the material structurally changes into simple carbon structures. Thishas been historically utilized for its absorptive properties, forexample in filtering wastewater as well as binding body toxins. Largeamounts of carbon are utilized for these purposes in numerousindustries. Furthermore, in certain instances, these structures maystore or conduct small amounts of electrical charges, whereasnoncarbonized cellulosic material does not conduct electricity. However,little, if any, carbonized material is currently used for suchelectrical property, as these materials still fall below transmissionrates for classically transmitting materials for transmitting electricalcharges or storing electrical charges, such as metallic based materials.

Carbon products based on hemp have heretofore been neglected. Thisneglect is due to numerous reasons including the significantdifficulties with the plant's mechanical structure, generation of stickyresin substances on the stalk during retting, its light mass anddensity, and presence of certain metabolites and cannabinoids, whichhave generally precluded its use. The processes and methods describedherein advantageously provide new methods and processes to generatemicron-sized particles from hemp-based cellulosic materials, which areadvantageously utilized in master batches for certain industrialprocesses, including fiber formation, film formation, and compositeformation, among other uses.

SUMMARY OF THE INVENTION

A process for generating a mixture of substantially homogeneous particlesize hemp char comprising: carbonizing hemp at a temperature of at least1100° C. under low oxygen conditions to create a char; milling said charto create a milled char having an irregular polyhedron shape;classifying the milled char using a classification system having atleast one gradient of 2 microns in size; and capturing the materialunder 2 microns in size.

In a preferred embodiment, material greater than 2 microns in size isadded to an unmilled char and remilled to reduce the size of thematerial, wherein preferably char of smaller than 2 microns iscollected. In a preferred embodiment, the char is processed through asingle classification system, wherein the classification gradient orscreen is 2 microns.

In a preferred embodiment, a classification system comprising at leasttwo gradients, a first of about 2 microns and a second of about 5microns; wherein material greater than 5 microns is removed, materialbetween 2 and 5 microns is captured, and material smaller than 2 micronsis captured.

In a preferred embodiment, material greater than 5 microns in size isadded to a char and remilled to reduce the size of the material.

In a preferred embodiment, the hemp is dried hemp, having been cut anddried for no more than 7 days.

In a preferred embodiment, the milling process comprises a dry millingprocess.

In a preferred embodiment, the milling process comprises a dry millingprocess using ball milling, air jet milling, ultrafine grinding,grinding, or combinations thereof.

In a preferred embodiment, the substantially homogeneous particlescomprise 99% of particles less than 2 microns in size.

In a preferred embodiment, the substantially homogeneous particles under2 microns in size comprise at least 50% of particles between 1 and 2microns.

In a preferred embodiment, the substantially homogeneous particlescomprise at least 70% of particles between 1 and 2 microns.

In a preferred embodiment, the substantially homogeneous particles under2 microns in size comprise at least 90% of particles between 1 and 2microns.

In a preferred embodiment, the milling process comprises a further stepof reducing the temperature of the char to less than −100° C.temperature; and milling the char at below −100° C.

In a preferred embodiment, the milling process, further comprises adrying process to reduce moisture content of the (milled material) toless than 5% water.

In a preferred embodiment, the milling process comprises a cryo millingprocess, wherein the mill is cooled to below −100° C., typically withliquid nitrogen or other liquid with temperatures lower than −100° C.

In a preferred embodiment, the milling process is a wet milling process,wherein the wet solvent and said wet solvent contains less than 5%water, and most preferably is a nonaqueous solvent.

In a preferred embodiment, a process for creating a mixture ofmicron-sized char having a specific classification size, comprising:charring a portion of hemp stalk at a temperature of greater than 1100°C. and collecting the charred hemp stalk; milling the charred hemp stalkfor a sufficient amount of time to generate a portion of micron-sizedhemp char having an irregular polyhedron shape; placing the portion ofmicron-sized hemp char into a classification system comprising at leastone classification screen of less than 10 microns; collecting theclassified fraction of micron-sized hemp char. In preferred embodiments,the hemp stalk is rough chopped before being charred. In preferredembodiments, the classification screen is less than 5 microns or lessthan 2 microns. In preferred embodiments, collecting the classifiedfraction of micron-sized hemp char includes collection of a desiredfraction and collecting a rejected fraction which is remilled to reducethe size of the hemp char.

In a preferred embodiment, a thermal energy process for generating aspecific classification size of nano particles of a cellulosic material,wherein said particles are charred and ground to a micron size and arecapable of having high conductive properties, which can be combined in amaster batch, for example with a polymeric substrate, which can befurther used to produce a fiber, yarn, or other material suitable forweaving, knitting or of binding these materials into fabrics.Preferably, the cellulosic material is hemp, and most preferable, thehemp comprises hemp stalk (which contains fiber and hurd). In apreferred embodiment, the micron size is less than 10, less than 5, orless than 2 microns in size.

A preferred embodiment is directed towards a process of carbonization ofhemp stalk in combination with a polymeric substrate, wherein thecarbonized hemp stalk is milled to less than 2 microns in size and iscombined in a master batch with a polymer, wherein said carbonized hempand polymer is capable of conductivity.

A preferred embodiment is directed towards a process of generating anonmetallic fiber capable of conductivity comprising: carbonizing hempin a furnace, said furnace being flushed with nitrogen and then andheated to at least 1100° C. in 60 minutes (14.6° C./min heat ramp);wherein the at least 1100° C. is held for at least 60 minutes; nitrogenflow is maintained over the heating and hold times to maintain a lowoxygen environment; removing the hemp from the furnace and cooling it toroom temperature; milling the cooled hemp to a particle size of lessthan 10 microns; combining the milled hemp into a polymer and extrudinga fiber. Preferably, wherein the particle size is less than 5 microns,and more preferably wherein the arithmetic mode particle size is between1 and 2 microns, and more preferably wherein the arithmetic meanparticle size is between 1 and 2 microns. In a preferred embodiment, themilled hemp is classified with a micron-sized classification screen andthe classified material is collected in fractions according to a desiredsize for master batch processing.

In preferred embodiments, the process wherein at least 90% of the hempparticles are of less than 10 microns, or more preferably wherein atleast 99% of the particles are of less than 10 microns. In preferredembodiments, wherein the milled hemp comprises between 1 and 50% of thetotal weight of an extruded fiber, more preferably, wherein the milledhemp comprises between 1 and 25% of the total weight of an extrudedfiber. In certain embodiments, wherein the milled hemp comprises between1 and 10% of the total weight of an extruded fiber, wherein the extrudedfiber comprises a polymer.

A further embodiment is directed towards a method of manufacturing anonmetallic fiber having a portion of carbonized particles and at leastone polymer comprising: carbonizing a portion of hemp material in afurnace, said furnace being flushed with nitrogen and then and heated toat least 1100° C. in about 60 minutes (at least 10° C./min heat ramp,with typical heating at 14.6° C./min heat ramp or greater); wherein theat least 1100° C. is held for 60 to 90 minutes; nitrogen flow ismaintained over the heating and hold times to maintain a low oxygenenvironment; removing the hemp from the furnace and cooling it to roomtemperature; milling the cooled hemp to a particle size of less than 10microns by a milling process for a period sufficient to reduce the hempinto an average particle size of less than 50 microns; combining themilled hemp with the at least one polymer, wherein the ratio of hempparticles to polymer is between 10:90 and 50:50; mixing the polymer andthe hemp particles; and extruding a fiber.

In a preferred embodiment, the average particle size is less than 25microns, and wherein at least 90% of all particles are less than 50microns in size, more preferably, wherein the average particle size isless than 10 microns and wherein at least 90% of all particles are lessthan 25 microns in size. In other embodiments, it is preferable togenerate a fiber wherein the average particle size is between 1 and 2microns and having an irregular polyhedron shape, and wherein at least90% of all particles are less than 10 microns in size, and mostpreferably wherein the average particle size is less than 2 microns andat least 95% of all particles are less than 2 microns in size.

A preferred embodiment comprises a carbonized hemp particle, having anaverage particle size of less than 25 microns, and at least 90% of allparticles of less than 50 microns, combined with a suitable polymer togenerate a fiber, yarn, or polymer for subsequent processing.

In a preferred embodiment, a process for creating a mixture ofmicron-sized charred hemp comprising: rough cutting a portion of hempstalk; charring the portion of hemp stalk at a temperature of greaterthan 1100° C. to create a char material; milling the char material tocreate a milled char having an irregular polyhedron shape; classifyingthe milled char with a classification system of less than 2 microns insize to create a fraction of hemp char particles; and collecting adesired fraction from the classification system of hemp char particles.

In a further embodiment, the process further comprising a first step ofdrying the hemp stalk before the rough cutting step.

In a further embodiment, the process wherein the temperature of greaterthan 1100° C. is held for at least one hour, and wherein the charringprocess is performed by addition of a nonoxygen gas to a heatingchamber.

In a further embodiment, the process wherein the milling is performed ina high energy ball mill.

In a further embodiment, the process wherein the classification systemincludes a classification of 2 microns or less.

In a further embodiment, the process wherein the desired fraction fromthe classification system is admixed with a polymer. In a furtherembodiment, the process wherein the desired fractions from theclassification system admixed with a polymer transmit an electricalcharge with a resistance of less than 100 Ω.

In a further embodiment, the process wherein the desired fraction fromthe classification system comprises a 95% specific classification sizeof less than 2 microns and a 95% bell curve of 1.5 microns.

In a further embodiment, a process for generating a mixture of nanosizedhemp char particles having a greater than 90% specific classificationsize of less than 2 microns comprising: charring a portion of hemp stalkwithin a furnace at 1100° C. or greater for a time sufficient to charthe material to create a charred material; collecting the charredmaterial and milling the charred material in a ball mill to create achar powder having irregular polyhedron-shaped particles; classifyingthe char powder in a classification system comprising at least one2-micron classification sieve, wherein char particles of less than 2microns pass through the 2-micron classification sieve; collecting theless than 2 microns char particles passing through the 2-micronclassification sieve and adding said less than 2 microns char particlesto a master batch with at least one polymer.

In a further embodiment, a process for creating a master batchcomprising a plurality of hemp char particles and at least one polymercomprising: carbonizing a portion of a hemp material in a furnace, saidfurnace being flushed with nitrogen and then heated to a temperature ofgreater than 1100° C.; wherein the temperature of greater than 1100° C.is held for at least 60 minutes; maintaining nitrogen flow over the atleast 60 minutes to maintain a low oxygen environment to create a char;removing the char from the furnace and allowing it to cool; milling thechar by a milling process for a period sufficient to reduce the charinto a plurality of particles having an irregular polyhedron shape andan average particle size of less than 2 microns to create char particlesof less than 2 microns; combining the char particles having an averageparticle size of less than 2 microns with the at least one polymer,wherein the ratio of char particles to polymer is between 10:90 and50:50; and mixing the at least one polymer and the char particles toform the master batch.

In a further embodiment, the process wherein at least 90% of all of thechar particles are less than 2 microns in size.

In a further embodiment, the process wherein the average particle sizeof all of the char particles is between 1 and 2 microns, and wherein atleast 95% of all of the char particles are less than 2 microns in size.

In a further embodiment, the process wherein the milling process is aball mill.

In a further embodiment, the process wherein the milling process is awet milling process. In a further embodiment, the process wherein thewet milling process comprises a nonaqueous solvent.

In a further embodiment, the process wherein the char particles havingan average size of less than 2 microns are classified to removeparticles of more than 2 microns in size.

In a further embodiment, a process of forming a plurality of charredhemp particle having more than 50% of particles formed between 1 and 2microns in size comprising: drying cut hemp stalk on a field for aperiod of less than 7 days; pyrolyzing the dried hemp stalk at atemperature of greater than 1100° C. to create a char; adding the charto a grinding vessel and grinding the char for a period of between 1 and16 hours to form a ground char having particles having an irregularpolyhedron shape; screening the ground char with a 2-micron screen tocreate a screened char of less than 2 microns; and capturing thescreened char of less than 2 microns.

In a further embodiment, the process wherein the grinding vessel is asteel vessel with steel grinding balls.

In a further embodiment, the process wherein the grinding is drygrinding.

In a further embodiment, the process wherein the grinding is wetgrinding. In a further embodiment, the process wherein the wet grindingis performed for a first duration of between 1 and 16 hours and isfollowed by a step of drying to create an agglomerated ground char andregrinding the agglomerated ground char in a dry grinding process.

In a further embodiment, the process further comprising separating thematerial resulting from the 2-micron screen into particles smaller than2 microns and particles larger than 2 microns and regrinding theparticles larger than 2 microns.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 depicts a flowchart of a process for cutting hemp from a field toprevent formation of substances.

FIGS. 2A and 2B depict a flowchart of a charring and classificationprocess for hemp.

FIG. 3 depicts a flowchart of a milling process for char.

FIG. 4 depicts an exemplar classification system.

FIGS. 5A and 5B jointly depict an expanded flowchart of a process forcreating fractions of nanoparticle hemp.

FIG. 6 depicts a flowchart of a wet milling process.

FIG. 7 depicts a flowchart for processing hemp.

FIGS. 8A and 8B depict images of carbon made in an irregular polyhedronshape for most effective use, labelled as “3D carbon” in the figure.

FIGS. 8C and 8D depict images of “flat carbon” particles found in priorart.

DETAILED DESCRIPTION OF THE INVENTION

Hemp has a long history of industrial use and was widely cultivated inthe world for its rough use for the fiber portion of the plant. Hemp hasmany advantages over other agricultural crops, namely, the plant itselfis resilient to weeds, it can be harvested 2-3 times a year and it doesnot need pesticides or herbicides to flourish. Its deep root systemmeans that hemp plants need much less nitrogen (fertilizer) and water toflourish compared to other crops like cotton. Moreover, farmers can usehemp plants as an alternative to clear fields for other crops. Theaverage hemp plant grows to a height of between six (6) feet to sixteen(16) feet and matures in approximately seventy (70) to one hundred ten(110) days, thus facilitating multiple harvest opportunities each yearin many areas of the world. A hemp crop has the potential of yielding3-8 tons of dry stalks per acre per harvest while remaining carbonnegative.

Hemp, like many dicotyledonous plants, contains a phloem (hurd) andfibers (bast fibers) around the phloem. Inside the bast fiber is thehurd, a wood-like portion of the hemp plant, which surrounds a hollowcore. In any given hemp plant, there is significantly more hurd biomassthan of fibers. Unfortunately, the use of the hurd has been shunned todate, even though it is the primary biomass of the plant. Manipulationand use of the hurd, therefore, would serve as a critical step in use ofthis cellulosic product that would otherwise become waste.

Fibers have been frequently utilized individually, which requires thatthe fibers are separated from the hurd by mechanical (for example,decortication), or chemical properties, and the fibers can then be usedfor any fiber materials, including textiles like carpet, yarn, rope,netting, matting, and the like.

The singular use of fibers, however, leads to large amounts of wastebyproduct, from the stalk and/or hurd and limits viability of the plantfor widespread cultivation. The hurd, by contrast, is relativelydifficult to use, and has previously only been used for rough processessuch as papermaking, particleboards, concrete mixtures, and constructioncomposites, as well as for animal bedding.

Widespread use of cannabis was dramatically reduced during the twentiethcentury due to the concern regarding the amounts of tetrahydrocannabinoids (THC) within the plants. However, there are a number ofdifferent strains/cultivars of the hemp plant that contain smaller andlarger amounts of the psychoactive compound, THC, and thus cultivationcan be optimized for the particular growth and THC content that isdesired, including plants with low to zero THC. Here, a fast growth rateand a high total biomass is desired, although any biomass may besuitable for use. These traits may be naturally derived through strainsand crossbreeding as known to those of ordinary skill in the art, orgenetically modified.

Ultimately, hemp functions as a carbon negative plant, making it highlyattractive for large scale use, especially where a downstream use can beidentified. These features make hemp an intriguing option forcultivation, but the many difficulties with the plant have precluded itsuse on any scale up to this point. What is missing from the hempecosystem are processes and methods for consumption of the hemp materialafter its growth, wherein the fibrous materials of the plant can beutilized in commercially viable enterprises.

Therefore, in an effort to pursue sustainable and environmentallyresponsible bio-char material, suitable for use in a variety of masterbatch processes, and as a replacement for the more expensive andtime/process intensive CNTs (carbon nanotubule) and graphenes in anynumber of commercial products, applicant has identified nanoparticlebio-char hemp-based materials and processes for generating the same.

Bio-char produced from the pyrolysis of cellulosic agricultural wasteresults in amorphous carbonized solids that exhibit similar electricalproperties of CNTs. Herein, the methods, processes, and products utilizecarbonized hemp as the cellulosic material to create carbonizedmaterials having particle size of less than 50 microns to incorporateinto materials, which can be utilized in master batches to generate spunfibers, spun or extruded fibers and films, composites, or through otherpostprocessing steps as known to those of ordinary skill in the art. Inpreferred embodiments the particle size is preferably less than 25microns, preferably less than 20 microns, preferably less than 15microns, preferably less than 10 microns, preferable between 5 and 10microns, preferably between 2 and 7 microns, preferably between 2 and 5microns, and most preferably below 2 microns. Once such material isgenerated, the micron-sized char can be utilized in any number of masterbatch protocols and postprocessing applications. Indeed, based upon theparticular processing steps, the materials can modify be imparted intomaterials generated from a master batch, such as a composite materialthat generates improved mechanical/structural properties as well asgenerating materials having certain electrical and/or conductiveproperties.

Hemp serves as the raw material for generation of the hemp-basedbio-char. In view of FIG. 1, a process is generally defined to grow hemp(1), cut hemp (2), dry hemp on (3), and rough chop the dried hemp (4).Several of these steps are further broken down into additional steps andprocesses in order to generate a nanoparticle sized bio-char havingsuitable properties for its downstream industrial use.

Growth of hemp (1) is predicated on simply growing biomass. Any of thevarious cultivars of the Cannabis sativa plant, and biowaste from hempgrowth can be utilized. In this manner, we can capture biomass fromother industries that are interested in processing seeds or leafy greensand utilize both the fibers and hurd from the stalk. Indeed, herein,processes are described that can utilize both the fibers and hurd inhigher value applications than the prior uses. The processes hereindescribe that it is preferential to utilize both the fiber and the hurdtogether, in order to generate a superior char material. Heretofore,hemp fibers were typically separated from the hemp hurd, and the fibersused for certain materials and the hurd and remaining biomass utilizedin low value applications, such as concrete fillers, animal bedding, andother applications, including simply being composted or burned as waste.However, the combined processing reduces waste and utilizes the fibersand hurd together an a more efficient and valuable process.

Cutting of the hemp (2) simply takes the growing hemp and cuts at thebase of the stalk or removes the hemp from the ground to begin thedrying process. Once the hemp is cut, the drying process begins (3)almost immediately, however, moisture is an enemy to the drying process.Accordingly, it may be suitable to cut the hemp (2) and allow them todry on the field for 0-7 days, then collecting them and finalizing thedrying process in a controlled environment. This can simply be within agreenhouse or warehousing space so that the material is not subjected torain or other moisture to facilitate drying and to prevent formation ofmold, rot, or other fungal growth.

Furthermore, as the hemp dries and the longer the hemp stalks remain onthe field the longer time, they have to undergo retting. The rettingprocess allows the hurd and fiber to naturally separate. However, as thehurd and fiber separate, the stalks become sticky with resin, and thisprocess makes it difficult, if not impossible to utilize the material ina continuous feed bio-char system, necessary for high throughput.Accordingly, the hemp material is preferably utilized within a specificwindow after harvest to prevent the retting and resin formation. Thissticky resin material, once formed, reduces the ability to efficientlychar the hemp, and further reduces the yield of milled char that isgenerated under 2 microns in size.

Therefore, to process the hemp most efficiently, it needs to bepreprocessed properly. Accordingly, a proper drying process is necessaryto ensure that the materials can be utilized in certain processingsystems. Thus, the preferred step is where the stalks should not lay ina cut state on the ground for more than a week. To do this properly,weather reporting and management of the cut material is necessary toprevent spoilage. In a preferred embodiment, the stalk would be cut anddried in a controlled environment and pyrolyzed, before retting takesplace. When retting does occur, the fiber and hurd may need to beseparated to allow for processing. This increases cost and time forprocessing and thus reduces sustainability. Furthermore, conductivity isgreater with the fiber and hurd pyrolyzed together, than when the fiberor hurd are pyrolyzed separately, as seen in Table 2, and thus thesingular processing of hemp stalk is important where conductivity isdesired in the char product.

Processing or rough chopping 4 of the hemp may include one or moresteps. In the simplest form, the dried hemp (3) is simply collected, andplaced into a furnace for carbonization. In other steps, for example, asin FIG. 7, the processing takes hemp stalks (71) and either rough chops(4), grinds (72), or strips (73) the stalks, or both grinding (72) andstripping (73) before adding the material to a furnace (11). Thisprovides a simple process to achieve material having an appropriate sizeto be charred in a furnace and achieve an even charred material. Thecharring process is to generate a carbon bio-char material, which can befurther milled, or ground as detailed in additional figures, includingFIGS. 2A, 2B, 3, 5A, and 5B.

Existing char is most commonly produced from coconut shell, peat, hardand soft wood, lignite coal, bituminous coal, olive pits and variouscarbonaceous specialty materials. In many industrial uses, char isactivated via chemical or steam processing. Activating char typicallyresults is a highly porous adsorptive medium that has a complexstructure composed primarily of carbon atoms. These materials are oftenused in large particle size for their absorptive properties. This is dueto the fact that the networks of pores in activated carbons are channelscreated within a rigid skeleton of disordered layers of carbon atoms,linked together by chemical bonds, stacked unevenly, creating a highlyporous structure of nooks, crannies, cracks and crevices between thecarbon layers, allowing for high binding of certain additionalmolecules.

However, the rough and large particle size materials are inconsistentwith their use in master batches, for example to be combined withpolymers for creation of fibers or for other applications that requirenanoparticles having nanosized particles within a mixture that are asubstantially homogeneous size. However, processing of the material intoa size of less than 10, 5, and/or 2 microns, and wherein a mixture ofparticles have a specific classification size is difficult to achieveand not achieved before the processes described in embodiments herein.

Process for Generating Micron Particles of Hemp Having a Precise SizeVariance

While certain cellulosic materials are both easily carbonized and thenreduced to a millimeter particle size, reduction to micron size wasfraught with great difficulty with hemp. First, the micron-sizedparticle is generated by the processes described herein, specificallytowards a particle size of less than 10, less than 5, and less than 2microns in size generates unique considerations. Second, the low densityof the material combined with the small size necessary for creatinghighly valuable materials renders the milling and classification processto be extremely difficult. As detailed in Table 1, the density of hempis dramatically less than typical char products, which impacts theability to mill and classify the resulting material. Several processeswere tried that resulted in varying levels of success with regard toconsistency and also to yield. The end product must both meet a minimumparticle size, but also be precise with respect to average size withinthe total particles within the mixture. Accordingly, we describe this aspecific classification size, i.e. one that has all particles with aprecise size (within an acceptable tolerance), or sometimes alsoreferred to as substantially homogeneous in size.

TABLE 1 Density of certain materials Density of Weight of Recoverableheat Dry Wood dry cord value of Cord Species (lb/ft³) (lb) (millions ofBTU) Aspen 27 2290 10.29 Cherry 36.7 3121 14 Hickory 50.9 4327 19.39 RedOak 44.2 3757 16.8 Hemp 8.74 741 3.33

In preferred embodiments, the process utilizes hemp stalk, however, awide range of hemp materials including: full hemp stalks, chopped fullhemp stalks, chipped full hemp stalk, full hurd, chopped hurd, chippedhurd, ground hurd, separated hurd and fiber, chopped separated hurd andfiber, chipped separated hurd and fiber, ground separated hurd andground separated fiber may be utilized for certain applications. Asdetailed below, and in Table 2, the combination of the hurd and fibersprovides a superior material for electrical properties.

Pyrolysis

When performing pyrolysis, bio-charring temperatures at preferablybetween about 600° C. to about 1500° C. and can be performed via batchor continuous flow processes. As seen in FIG. 2A, rough chopped hemp (4)is added to a furnace (11) and then heated to more than 1100° C. (13).An intermediary question is whether the hemp needs to be chemicallyactivated (19), and if yes, then it is chemically activated (20) andthen added to the furnace (11). In particular, the heating process isdone at low oxygen percentages, this is to prevent the completecombustion of the material, as known to those of ordinary skill in theart. Accordingly, the chamber is filled with one or more inert gassesduring the char process. While a temperature of at least 600° C. issufficient to char the material, it leads to uneven burn of the materialand uneven charring. More importantly, processing at the low end of thetemperature scale leads to low amounts of conductivity on its own.Furthermore, in subsequent processing of the material into nanoparticlesizes, the inconsistent char makes it impossible to effectively grind toa substantially homogeneous particle size with any reasonable yield.Pyrolysis from about 1100° C. to about 1500° C. not only produces anevenly charred material, but also produces a material with higherconductivity than if processed at a lower temperature. Thus, whenprocessing above 600° C. but below about 1100° C. (51), FIG. 5A detailsone possible method, wherein it is necessary to further activate thecarbon in order to modify the cellular structure through an activationstep, which is typically steam activation (14) or chemical activation(20). This activation step is not as efficient as high temperaturepyrolysis.

The process herein is unique in several ways. First, as defined in FIG.2A, the activation process is preferably carried out at 1100° C. orgreater (13) in low oxygen conditions. Most bio-charring (charcoalformation) is not carried out at such high temperatures. Furthermore,the physical characteristics of the hemp plant make the subsequentprocessing of micron-sized particles exceedingly difficult at anysuitable yield, as detailed in Table 1, which shows that hemp is a muchlower density than other common cellulosic materials used for makingchar in that the lightweight and low-density nature of hemp makes itmore difficult to process into a uniform and small particle sizenecessary for its use in certain materials described herein. Inparticular, the particle size as well as the particle shape areimportant.

Interestingly, the carbon utilized in these processes and in, forexample, downstream manufacturing processes are advantageous when theyhave a three-dimensional shape instead of the typical flat carbonmaterials. Typical carbon materials are long and flat, and while theyhave a minimal three-dimensional characteristic, the length and/or widthare typically 100 to 10,000 times the height (think of graphene). Whensuch particles are compressed, they are not regularly ordered and sosome particles are oriented vertically, others horizontally, and yetothers in every odd direction. Because of the great difference in theparticle shape, this yields very fine irregularities in the products.

In comparison to the typical long and flat particles, the process hereincreates particles that are more consistent in dimensions between thelength, width, and height, which are an irregular polyhedron shape. Thisresults in an irregular polyhedron particle that, while not having anorganized shape, has a dimension in each of the three (3) axes (x, y, z)that is closer in size than the typical graphene particle. Thus, where aflat carbon (graphene) of the prior art would have (by example only) alength of 5 microns, a width of 5 microns, and a height of 0.01 micron,for example, the claimed carbon would not have the same discrepancy withregard to differences between the longest and shortest axes. An exampleparticle could have a length of 1.5 microns, a width of 1.0 microns, anda height of 0.4 microns, with many facets. Accordingly, this shape is anirregular polyhedron, and the particles formed are irregular polyhedronparticles.

FIGS. 8A and 8B depict images of the irregular polyhedron particles,labelled as “3D carbon,” while FIGS. 8C and 8D depict images of “flatcarbon” graphene. Notably, the irregular polyhedron carbon is of smallersize, is more consistent in the size in relation to the other particles,and is less flaky (i.e., the material is not as long and thin) as theprior art carbon. The hemp-based material thus has a narrower bell curveand the particles themselves are more consistent in their size ratiobetween the major axis (the longest length) and the minor axis (theshortest length) for each particle on average as compared to the priorart. This feature is significantly important to ensure the tightesttolerances when using the irregular polyhedron shaped particles indownstream processes, such as in the manufacture of fibers.

Steam Activation

While temperatures above 1100° C. are preferred, it may be optimal tochar at lower temperatures in some embodiments and activate the char.This process may include chemical activation or steam activation, thoughsteam activation, if any activation is performed, is preferred. Asdepicted in FIG. 5A, when heating to a temperature of greater than 600°C., but between 600° C. and 1100° C., we need to activate (14) thematerial. The activation stage of the char enlarges the pore structure,increases the internal surface area, and makes it more accessible.During steam activation, the carbonized product is activated with steamat a temperature between 600° C. and 1200° C. The chemical reactionbetween the carbon and steam takes place at the internal surface of thecarbon, removing carbon from the pore walls and thereby enlarging thepores. The steam activation process allows the pore size to be readilyaltered and carbons can be produced to suit specific end uses.

Chemical Activation

As opposed to steam activation, chemical activation involves theprocessing of and mixing raw material with an activating agent, to swellthe char and open up the cellulose structure before pyrolysis. Preferredchemical activation agents include an acid, base, or salt, such asformic acid, acetic acid, propionic acid, succinic acid, oxalic acid,lactic acid, malic acid, benzoic acid, phosphoric acid, nitric acid,hydrochloric acid, hydroiodic acid, nitric acid, sulfuric acid,perchloric acid, bases, such as sodium hydroxide, barium hydroxide,strontium hydroxide, and other sales such as calcium chloride, zincchloride and others as known to those of ordinary skill in the art.Accordingly, the process inquires if chemical activation is necessary(19), and if yes (20), then an activation chemical is added. Once theraw material is impregnated with the chemical, the impregnated materialis carbonized by adding to a furnace (11), often at the lower end of thetemperature scale, 600°-900° C., to yield activated carbon. Oncarbonization, the chemical acts as a support and does not allow thechar produced to shrink. It dehydrates the raw material resulting in thecharring and amortization of the carbon, creating a porous structure andan extended surface area.

Activity is controlled by altering the proportions of raw material toreagent used. Activity increases with higher reagent concentration andis also affected by the temperature and cook time.

Accordingly, as defined in FIGS. 2A and 5A, a decision tree at theheating/activation point is necessary (19). If heating to above 1100° C.(13) then no activation is necessary. If heating to less than 1100° C.,a decision about the activation process is necessary, with an initialchemical loading step (20) necessary before charring, and a steamactivation step (14) (FIG. 5A) is necessary if no chemical activation iscompleted. In each case, once a temperature is determined, the materialis placed in a low oxygen environment and temperature steadily increasedand held for a sufficient amount of time to char the material.Typically, this is 2-12 hours.

When activating, high temperature activation is preferred, with steamactivation and chemical activation as other preferred embodiments. Hightemperature activation is the most sustainable, but each are sufficientto open the surface area of the char, which improves moisturemanagement, antistatic, friction, and aesthetic characteristics. Indeed,when the material is processed, one gram of carbon results in 32,000square feet of surface area.

Accordingly, the process of pyrolyzing and activating the hemp materialis important for imparting certain physical properties to the material.This is optimized by processing hurd and fibers together, at atemperature of above 1100° C. or higher, which yields improvedelectrical or conductive properties as depicted in Table 2, below.Indeed, while it is commonly known that charcoal is a poor conductor ofheat (e.g., walking on coals) and electricity, Applicant has generated aprocess and material that is of a substantially homogeneous size andstructure that conductive and electrical properties are generatedthrough irregular polyhedron-shaped particles. Indeed, it is these smallsizes and structure that are able to suitably generate and carry certainelectrical charges under certain circumstances.

Table 2 shows a summary of electrical properties. Applicant tested theability to transmit a charge through a material comprising 20%carbonized hemp material. The carbonized hemp material and temperatureof char was varied to determine an optimal process for manufacture, asdetailed in the results in Table 2. In sum, a combined hurd and fibermaterial, charred at greater 1100° C. or greater showed improved resultsas compared to those of fiber or hurd alone or charred at below 1100° C.

TABLE 2 Comparison of Materials for Electrical Properties Temperature ofElectrical Material Furnace (° C.) Property Hurd 600 Weak Hurd 900 WeakHurd 1100 Weak Fiber 600 Weak Fiber 1100 Weak Combined Hurd/Fiber 600Weak Combined Hurd/Fiber 900 Weak Combined Hurd/Fiber 1100 Best CombinedHurd/Fiber 1200 Same as 1100° C.

Therefore, in bio-charring hemp materials, the hemp material is heatedin an inert (low oxygen conditions, typically through addition ofanother gas) atmosphere so that dehydration and devolatilization of thecarbon occur. Optimization of this process utilizes a combination ofhurd and fiber at a temperature of more than 1100° C. Carbonization ofthe hemp then reduces the volatile content of the source material tounder 20% and yields a coke. The coke is then further manipulated bymilling the material before it can be used with polymeric substrates indownstream master batches.

Because of the brittle nature of the carbonized material, it can bedirectly milled (15) into fine powders having particle sizes in themicron dimensions for suitable use as an irregular polyhedron particlein composite materials. For example, milling (15) by placing thecarbonized material into a mill, will result in rapid reduction ofparticle size into an irregular polyhedron particle powder of having aparticle size of less than 2 microns in the largest axis of theirregular polyhedron particles.

Milling

Continuing with FIGS. 2A and 2B, after heating to a temperature ofgreater than 1100° C., the process continues in FIG. 2B to milling (15).Milling or grinding of the material to a specific classification sizecreates a better product with greater uses than products that do nothave a specific classification size. In certain embodiments, thedistribution of particle sizes within a range may also be defined by anarithmetic mean, arithmetic mode, etc. As used herein, the term“specific classification size” refers to a percentage of particleswithin a certain given point as compared to the classification size. Forexample, a specific classification size of 2-5 microns, means that atleast 90% of all particles are between 2 and 5 microns. The micron sizerefers to the length of the largest axis, i.e., within the x-, y-, andz-axes of the irregular polyhedron particles. More preferably, a 95%specific classification size, a 99%, or a greater than 99% specificclassification size means that 95%, 99%, or more than 99% of particlesare between 2 and 5 microns in size, respectively.

Furthermore, the specific classification size can be further narrowed bydefining a specific micron size and bell curve. For example, a 99%specific classification size of 2-5 microns and a 95% 3.5-micron bellcurve means 99% of particles are within 2-5 microns and that 95% of allparticles are within 2 standard deviations from 3.5 microns. This isintended to make sure that the irregular polyhedron particles areprecise with regard to their size within a plurality of particles, witha goal that size is homogeneous among all particles. The bell curve maybe a 50%, 75%, 90%, 95%, 99%, or more than 99% bell curve. In essence, atighter bell curve gives a particle size that is more homogeneous insize. Having something be more homogeneous leads to a better resultingproduct, especially for irregular polyhedron particles of less than 5microns and certainly of less than 2 microns in size. In a preferredembodiment, the irregular polyhedron particles have a 90% specificclassification size of less than 2 microns, with a 90% bell curve at 1,1.25, or 1.5 microns. This results in a 90% specific classification sizeof less than 2 microns, a 90% bell curve at 1.5 microns, and results inan average mean particle size of between 1 and 2 microns.

The classification process, e.g., in FIGS. 2A, 2B, 3, 4, 5A, and 5Bproved especially difficult at a suitable yield and to generate thespecific classification size of less than 2 microns suitable for use incertain downstream processes. To form a material with 90% of particlessmaller than 2 microns, with the average mean particle size between 1-2microns, a screening or classification process is utilized to removeparticles greater than 2 microns after the material is milled. Forexample, as detailed in FIG. 2B, the milling step (15) is followed by aclassification step (16), and wherein desired fractions (17) arecaptured, and any rejected fractions (18) are remilled to achievesmaller particle sized.

To generate the suitable fractions and to form suitable sized particles,the process preferably utilizes a ball mill, with the possible additionof one additional step. Ball mills add material to a container andinclude one or more balls within the container, which is then oscillatedto shake the balls and material together. This process crushes thematerial from its brittle state into the irregular polyhedron particles.FIG. 3 details an embodiment of a milling process, which, begins bycapturing charred hemp (21), which is then added to a ball mill (31).The charred hemp is ground or milled in the ball mill (32). The materialis then classified (16), desired fractions are captured (17), andrejected fractions (18) are readded to the ball mill (31) to go throughthe process again. The desired fractions are added to master batches(34) for downstream processing.

In certain embodiments, it is suitable to cryo mill (33) the charredhemp. Cryo milling involves milling the material under liquid nitrogenor other material, typically at a temperature of less than −100° C. Byreducing the temperature of the material, we lower the charred hempbelow a point to which the material has become brittle, thereby millingat this temperature increases the fracture of the charred hemp intonanoparticles for our applications, especially those below 10, below 5,and below 2 microns in size. The cryo milling process can be excluded,replace normal milling, or be completed in addition to regular milling.

Finally, the particles are sorted by size. Accordingly, in FIG. 2B, thematerial is milled (15), and then classified (16). The classificationprocess then separates the material into suitable fractions and thedesired fractions are captured (17). Rejected fractions (18) are addedback to the mill (15) to remill then to a smaller size. Preferredcaptured fractions include less than 2 microns (55), for use inapparel/fibers and fabric uses (58). Additional fractions between 2-5microns (53) can be used for, e.g., home furnishings (56). For fractionsbetween 5-10 microns (54) can be utilized for industrial fibers/fabricuses (47). For fractions greater than 10 microns (52), an exemplar useis with certain composites (59). These fractions are advantageouslyadded to master batch polymerization (60) for such downstream uses asappropriate.

An example of a classification sieve set is defined by FIG. 4, a firstclassification container (41), with a first classification screen (42)captures a first material (52), a second classification container (43),and a second classification screen (44), captures a second material (54)a third classification container (45), and a third classification screen(46), captures a third material (53), and finally a fourth container(47), that captures any material (55) that falls through the thirdclassification screen (46).

As an example, the first classification screen is 10 microns, the secondclassification screen is 5 microns, and the third classification screenis 2 microns. By adding the charred and milled hemp to the firstcontainer (41), any material (52) greater than 10 microns will becaptured in the first container (41). This allows material (54) smallerthan 10 microns and larger than 5 microns to be captured in the secondcontainer (43). Material (53) smaller than 5 microns and larger than 2microns is captured in container (45), and finally all the material (55)smaller than 2 microns passes through the third classification screen(46) and into the fourth container (47).

Yield for the 2-micron size can be optimized based on the time of themilling process. Optimized yield is at least 50% of the material at lessthan 2 microns in size. For example, starting with 10 kg of char, wouldyield at least 5 kg of material of less than 2 microns in size. A yieldof this amount was surprisingly difficult to achieve, as is detailed inthe following experiments.

In preferred embodiments, the preferred particle size is 2 microns.Creation of irregular polyhedron particles at this size is optimized forcreating improved fibers suitable for use in nearly all applications.However, reaching this size with the irregular polyhedron particle shapewas very difficult. Formation of less than 2-micron-sized irregularpolyhedron particles can be achieved by manual grinding of material witha mortar and pestle. However, use of this system is impracticable forcommercial applications. Even so, such process leads to wide ranges ofparticle sizes that need to be screened to obtain the useable materialat the 2-micron size.

In order to move to commercial applications, milling may include any ofgrinding, such as air jet grinders, wet processors, small batch highenergy ball grinders, dry agitated media mills, pressure grinding, andother grinding and milling processes as known to one of ordinary skillin the art. Such grinders may rotate at a given RPM or oscillate at aparticular frequency (Hz). The grinding process included times fromabout 1 hour to about 16 hours, with all times in between. Commercialattempts at grinding to 2 microns were suggested to be easilyobtainable, yet actual processing to this size within acceptabletolerances (precision) and yields proved difficult.

Thus, a preferred embodiment follows the process according to FIGS. 2Aand 2B, or FIGS. 5A and 5B. For example, FIGS. 5A and 5B detail cut hemp(2), which is dried (see FIG. 1) and rough chopped (4). The roughchopped hemp (4) is determined to need chemical activation or not, withyes then chemically activating (20) the material, and no, adding itstraight to the furnace (11). Where the temperature is heated to greaterthan 600° C. (12), and preferably greater than 1100° C. (13). If thetemperature is between 600° C. and 1100° C., then the product must beactivated (14), either chemically, as above (20), or steam activated(14), as described herein. Then the material can be milled (15). FIG. 5Bthen details adding the material to a ball mill (31), milling for asufficient time in a ball mill (32), and classifying the material (16)after milling within the ball mill. Classified material is eitherrejected fractions (18), greater than 10 microns (52), 5-10 microns(54), 2-5 microns (53), or less than 2 microns (55). Exemplar uses ofsuch material are defined as composites (59), industrial fibers/fabricuses (57), home furnishings (56), or apparel fibers/fabric use (58).This is determined based on the possible denier size of a fiber, whichdirectly corresponds to the micron size of the char, and the formationof the less than 2-micron-sized char (55) for the apparel fibers/fabricuse (58) being a primary end point for the bio-char.

A primary issue in generating the irregular polyhedron shaped particlesof substantially homogeneous particle size is that hemp carbon has alighter bulk density than other cellulosic carbon materials, so in drygrinding, the carbon floats around in the dry grinding mills, making itdifficult to actually grind the material. Accordingly, several differentprocesses and methods were tested to optimize the milling andclassification process in order to generate suitable yields of the lessthan 2-micron-sized material.

EXPERIMENT 1: HAND MILLING WITH MORTAR AND PESTLE

10 grams of carbonized hemp made from hemp stalk (hurd and fiber)material was placed into a mortar and hand ground with a pestle.Grinding was performed for approximately 3 minutes, and the material wasturned from small lumps into a fine powder. The powder material was thenreviewed under a microscope for size. While a large portion of materialwas sufficiently ground to small sizes, there were significant amountsof material at larger sizes, due to incomplete processing. To quantifythe amount of material below 2 microns, a 2-micron screen was utilizedand approximately 45% of the material was below 2 microns.

The material larger than 2 microns was then reground for an additional 3minutes and rescreened. An additional portion of material was generatedbelow 2 microns. This process was repeated several times, with anaverage of 6.5 grams of material being less than 2 microns after twogrindings, and a total yield of about 80%, meaning that about 20% ofmaterial was lost or not ground below 2 microns in the hand process, dueto spilling, aeration of the particles through the screening andtransfer processes, etc.

EXPERIMENT 2: DRY MILLING WITHOUT CLASSIFICATION

Experimental grinding included dry grinding in agar jars, with 3 mm agarballs. This provided a grind wherein about (“about” meaning ±10% of anumber) 50% of the char material was ground below 2 microns. Timing forgrinding in this application typically was between 3 and 7 hours, withalmost no difference in the resulting particle size when increasing from3 to 7 hours. Furthermore, moving to steel jars and balls also resultedin similar processing. About 50% of the material is greater than 2microns, and of the 50% larger than 2 microns, the size varied all theway up to 100 microns in size, and so it was determined that thisprocess alone, was insufficient to generate a material of uniformmaterial of less than 2 microns in size and also met any precisiontolerances for use in a master batch.

Among four tests, three used agar jars, with a total amount of materialbelow 2 microns at 47%, 51% and 52%, and the steel jar at 49%.

EXPERIMENT 3: DRY MILLING WITH SINGLE STEP CLASSIFICATION

As Experiment 2, above, failed to generate a material having highuniformity of size, a classification step was added to aid in sortingmaterial by size. Experimental grinding included dry grinding in agarjars, with 3 mm agar balls. This provided a grind wherein about 50% ofthe char material was ground below 2 microns as in Experiment 2. Timingfor grinding in this application typically was between 3 and 7 hours,with almost no difference in the resulting particle size when increasingfrom 3 to 7 hours. Milling at 3 hours, 5 hours and 7 hours, eachresulted amounts of material at about 50% of the total below 2 micronsin size. Starting with a process that generated 50% of the materialbelow 2 microns allowed use of a screening or classification system tocollect the 2-micron and below material, and the remaining 50% of largermaterial above 2 microns is remilled in a subsequent processing. Thisprocess is repeated until a sufficient quantity of 2 microns or smallermaterial is produced. When screening at such small sizes, some materialof larger size may pass through the screens, but about 70%, 80%, 90% ofthe material, and preferably 95%, and most preferably 99% of thematerial is 2 microns or smaller, to achieve a mixture of particles withhigh precision and specific classification size and bell curve. Forexample, a 99% specific classification size of less than 2 microns and a95% 1.5-micron bell curve means that 95% of all particles are within 2standard deviations from 1.5 microns was achieved, with a yield of about50%, with yields increasing after remilling material. This process isoptimized for use when a nonaqueous solvent is not suitable for use withthe master batch.

EXPERIMENT 4: DRY MILLING WITH MULTISTEP CLASSIFICATION

The process of Experiment 3 was repeated, but instead of a single2-micron screen, a three-screen process, e.g. as depicted in FIG. 4 wasutilized. The multiscreen process allowed for capture of additionalfractions, but there is a small loss of yield, due to some of thematerial being trapped in larger screens and other losses. This loss wasless than 2%, and so no additional process was used to push materialthrough the screens, e.g. compressed air, or vacuum. A shaking systemwas utilized to gently coerce the material through the classificationscreens to capture material. Yield resulted in just about 50% ofmaterial below 2 microns after a first pass through the classificationprocess. Regrinding of the material generated additional material;however, it is most advantageous to simply add the larger material to anew batch of carbonized material, and continually generating 60% of thetotal mass per run. This process is optimized for use when a nonaqueoussolvent is not appropriate for the master batch, and where differentsizes of materials are desired for different applications or masterbatches.

EXPERIMENT 5: WET MILLING WITH WATER

Wet Milling with Water: Wet milling adds water to the milling chamberbefore undergoing the milling as detailed in Experiment 3. This isdetailed in FIG. 6, where we add hemp material to the furnace (11). Weadd this charred material to a mill (61), and we then add water to themill (62). The material is then wet processed (63), where the ratio is60% water to 40% hemp char and processed for between 3-7 hours at 30 Hz.The wet material then needs to be spray dried (64) and milled againbecause of reagglomeration, and then classified (65). The results of wetmilling produce a highly uniform material, with production of more than95% of the captured material below 2 microns. However, thesustainability numbers took a dramatic decrease as compared to any ofthe dry milling processes, as the yield was 50% lower than the dryprocesses (total yield about 25%). The reduction in yield is becauseafter wet processing, the material needed to be spray dried (64), andthis resulted 50% or more of the carbon being lost in the various tests.Indeed, the spray drying process simply blows away the smallestparticles, which requires them to be captured from a debris field in thespray drying process. This introduces expense and difficulty in captureof the material. Furthermore, classifying the material proved difficult,and required a further remilling (66) under dry conditions, to reduceagglomeration of the previously wet-ground char. Each step is bothexpensive and resulted in loss of material that becomes unsustainablefor production.

EXPERIMENT 6: WET MILLING WITH A NON-WATER SOLVENT

The process of milling with a liquid, but not water, is simplified, asdepicted in FIG. 6. As depicted in FIG. 6, the material, instead ofbeing milled with water, then dried, and then classified, is simplymilled with the liquid solvent (66), milled (67) and then can bedirectly added to the master batch (68). The wet milling process issuperior in many applications, as it reduces the ability of the hemp to“float” in the milling process and yields greater amounts of material ator below 2 microns, and in fact, more than 50% of the material is below1 micron in size, and more than 90%, more than 95%, and more than 98% ofthe material was below 2 microns. Classification processes may still becarried out with the liquid, to remove those materials above 2 microns,but this step is not necessary in optimized protocols as it reducesyield. Using an alcohol solvent, acetone, an oil, other polar ornonpolar solvents, or combinations thereof, allowed the milled materialto be directly added to a master batch. Preferably, an oil or solventcompatible with the final master batch is utilized. Total yield ofmaterial and material below 2 microns in size is greatest using thisprocess, as little is lost in the milling and classification processesthat are present with the fine and dry materials. This process isoptimized, where such non-water solvents are suitable for addition intothe master batch.

EXAMPLE 7: SUS-1100° C. BURNING

HEMP CARBONIZATION: A Thermo Scientific™ Lindberg/Blue M™ tube furnacewith a 1000° C. temperature capability is used which can accommodate a1″ outer diameter tube. The stainless steel tube is fitted withcompression fittings and a ⅛″ nitrogen line. Seven to 10 g ofhomogeneously sized hemp stalk is packed into the tube, flushed withnitrogen, and heated from 25° C. to 1000° C. in 60 minutes (14.6° C./minheat ramp). The 1000° C. is held for 60 to 90 minutes. Nitrogen flow ismaintained over the heating and hold times.

Additional Experimental Parameters

TABLE 3 Yield Under 2 microns Total with One Process Mill Details YieldMilling Hand Mortar and pestle for 3-5 minutes 80 45 milling Ball mill3-hour milling, no classification 80 50 Ball mill 5-hour milling, noclassification 78 51 Ball mill 7-hour milling, no classification 75 51Ball mill 3-hour milling, 1 step classification 80 50 Ball mill 3-hourmilling, multistep classification 79 53 Wet mill 3-hour wet milling inwater and spray 28 25 drying Wet mill 3-hour wet milling in oil 92 92Wet mill 3-hour wet milling in ethanol 92 92 Wet mill 1-hour wet millingin ethanol 93 90

Carbon Nanoparticle

Once the material is charred, activated (if necessary), and milled to anappropriate nanoparticle size within a specific classification it can beappropriately utilized in downstream processing such as a master batch.For example, it is preferred to use the material within polymer orparticle formation to modify physical characteristics, such asmechanical characteristics (strength, weight, rigidity, etc.), orelectrical properties. Factors that improve electrical conductivityinclude high temperature pyrolyzation, structure, and porosity. Wherethe particles are small and have an irregular polyhedron shape, theirsurface area is larger than otherwise and allows for greater contactbetween irregular polyhedron particles to generate or store charges.High structure means that the carbon agglomerates to form long andbranched chains. Such a structure is ideal for conductive compounds.Higher particle porosity enables better electrical conductivity, andthis is generated through increased temperature processing, (i.e., 1100°C. or higher).

Accordingly, in a preferred embodiment, the charred hemp is milled: Thehemp char is milled to between 1-2 microns in size to create a finepowder of irregular polyhedron particles. Furthermore, the medianparticle size is preferably between 1-2 microns, and having more than50, 60, 70, 80, 90, or 99% of the particles at a size of less than 2microns. When using larger micron sizes, the size variability mayincrease slightly. However, at this preferred less than 2 microns insize, precision with regard to particle size of the material seekspercentages at less than 2 microns as indicated. Preferably, the processincludes a screening or classification process, which removes particleslarger than 2 microns or generates fractions to create a material of asubstantially uniform particle size. The 2 microns and less particlesare optimized for use in making materials specifically with certainpolymers, and the larger particles are put through the grinding processagain to obtain smaller particles. The processes described herein, allowfor higher yields of the material, while generating at least 60% of thecharred hemp at less than 2 microns in size, with more than 50%, 60%,70%, 80%, 90%, 95%, and 99% of all particles between 1 and 2 microns insize of the less than 2-micron size fraction.

A preferred embodiment comprises a wet milling process comprising:processing a portion of hemp; charring said hemp at a temperature ofgreater than 1100° C. under low oxygen conditions to yield a char;placing said char into a mill with a portion of a solvent comprisingless than 5% water; milling said material for at least 30 minutes togenerate a nanoparticle char; combining the nanoparticle char with apolymer into a master batch. In a preferred embodiment, the solvent isan oil, a branched or linear alcohol, preferably a C₁-C₁₀ alcohol;acetone, or another suitable nonaqueous solvent.

A preferred embodiment comprises between 1 and 50 percent of a pluralityof hemp particles, said plurality of hemp particles having an averageparticle size between 1-2 microns, and between 99 and 50 percent of atleast one polymer. The materials are admixed until uniform into a masterbatch to be formulated into a subsequent material.

A preferred embodiment is directed towards a method of producing a hempchar material for master batch, comprising carbonized cellulosicmaterial, specifically from hemp, comprising: carbonizing a cellulosicmaterial by charring the cellulosic material at a temperature of about900° C. under nitrogen for 60-90 minutes; reducing particle size of thecharred cellulosic material by milling the material to a particle size,with 90% of particles of less than 10 microns, preferably with anaverage particle size of about 1-2 microns; combing a portion of theparticles with at least a second component wherein said particles andsaid second component can be formed into a master batch for subsequentformation of materials. In preferred embodiments, the method abovecomprises between about 1 to 50% of the hemp particles with about 99 to50% of at least one polymer.

What is claimed is:
 1. A process for creating a mixture of micron-sizedcharred hemp comprising: rough cutting a portion of hemp stalk; charringthe portion of hemp stalk at a temperature of greater than 1100° C. tocreate a char material; milling the char material to create a milledchar having an irregular polyhedron shape; classifying the milled charwith a classification system of less than 2 microns in size to create afraction of hemp char particles; and collecting a desired fraction fromthe classification system of hemp char particles.
 2. The process ofclaim 1 further comprising a first step of drying the hemp stalk beforethe rough cutting step.
 3. The process of claim 1, wherein thetemperature of greater than 1100° C. is held for at least one hour, andwherein the charring process is performed by addition of a non-oxygengas to a heating chamber.
 4. The process of claim 1, wherein the millingis performed in a high energy ball mill.
 5. The process of claim 1,wherein the desired fraction from the classification system is admixedwith a polymer.
 6. The process of claim 1, wherein the desired fractionfrom the classification system comprises a 95% specific classificationsize of less than 2 microns and a 95% bell curve of 1.5 microns.
 7. Aprocess for creating a master batch comprising a plurality of hemp charparticles and at least one polymer comprising: carbonizing a portion ofa hemp material in a furnace, said furnace being flushed with nitrogenand then heated to a temperature of greater than 1100° C.; wherein thetemperature of greater than 1100° C. is held for at least 60 minutes;maintaining nitrogen flow over the at least 60 minutes to maintain a lowoxygen environment to create a char; removing the char from the furnaceand allowing it to cool; milling the char by a milling process for aperiod sufficient to reduce the char into a plurality of particleshaving an irregular polyhedron shape and an average particle size ofless than 2 microns to create char particles of less than 2 microns;combining the char particles having an average particle size of lessthan 2 microns with the at least one polymer, wherein the ratio of charparticles to polymer is between 10:90 and 50:50; and mixing the at leastone polymer and the char particles to form the master batch.
 8. Themethod of claim 7, wherein at least 90% of all of the char particles areless than 2 microns in size.
 9. The method of claim 7, wherein theaverage particle size of all of the char particles is between 1 and 2microns, and wherein at least 95% of all of the char particles are lessthan 2 microns in size.
 10. The method of claim 7, wherein the millingprocess is a ball mill.
 11. The method of claim 7, wherein the millingprocess is a wet milling process.
 12. The method of claim 11, whereinthe wet milling process comprises a nonaqueous solvent.
 13. The methodof claim 7, wherein the char particles having an average size of lessthan 2 microns are classified to remove particles of more than 2 micronsin size.
 14. A process of forming a plurality of charred hemp particleshaving more than 50% of particles formed between 1 and 2 microns in sizecomprising: drying cut hemp stalk on a field for a period of less than 7days; pyrolyzing the dried hemp stalk at a temperature of greater than1100° C. to create a char; adding the char to a grinding vessel andgrinding the char for a period of between 1 and 16 hours to form aground char having particles having an irregular polyhedron shape;screening the ground char with a 2-micron screen to create a screenedchar of less than 2 microns; and capturing the screened char of lessthan 2 microns.
 15. The process of claim 14, wherein the grinding vesselis a steel vessel with steel grinding balls.
 16. The process of claim14, wherein the grinding is dry grinding.
 17. The process of claim 14,wherein the grinding is wet grinding.
 18. The process of claim 17,wherein the wet grinding is performed for a first duration of between 1and 16 hours and is followed by a step of drying to create anagglomerated ground char and regrinding the agglomerated ground char ina dry grinding process.
 19. The process of claim 16 further comprisingseparating the material resulting from the 2-micron screen intoparticles smaller than 2 microns and particles larger than 2 microns andregrinding the particles larger than 2 microns.